摘要
将纳米金刚石进行热退火反应得到尺寸约5 nm的准球形纳米洋葱碳(CNOs),利用浓H_(2)SO_(4)/HNO_(3)混合酸的强氧化性在CNOs表面引入羧酸基团,得到羧酸化CNOs(C-CNOs).进一步对C-CNOs进行酰基化和亲核取代反应,制备了高度磷酸化的CNOs(P-CNOs).高分辨透射电子显微镜(HRTEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)分析结果表明—COOH和—PO_(3)H_(2)基团的引入,P-CNOs的离子交换量(IEC)达到1.85 mmol/g.P-CNOs与磺化聚芳醚砜(SPAES)共混后,通过溶液浇铸法制备了一系列均质、完整且致密的SPAES/P-CNOs复合膜.吸水溶胀、抗氧化稳定性、质子传导率和电池性能等测试结果表明,与纯SPAES膜相比,SPAES/P-CNOs复合膜的各种性能均有提升.这是由于P-CNOs上的—COOH和—PO_(3)H_(2)基团与SPAES上的—SO_(3)H基团通过氢键相互作用,不仅可以形成更加稳定的网状结构,增强复合膜机械性能和化学稳定性,还可以促进H+在膜内的转移,提升其传导率.在90℃时,SPAES/P-CNOs-1.5的质子传导率高达220 mS/cm;在80℃/100%相对湿度(RH)下,SPAES/P-CNOs-1.5复合膜在H2/O2燃料电池中的最大功率密度达到了650 mW/cm2,与纯SPAES膜相比提高了36%,且机械性能好,热-尺寸-化学稳定性高,具有很好的应用前景.
Quasi-spherical carbon nano-onions(CNOs)with a size of ca.5 nm were synthesized via thermal annealing of nanodiamonds.Subsequent oxidation using concentrated H_(2)SO_(4)/HNO_(3) introduced-COOH groups,yielding carboxylated CNOs(C-CNOs).Further functionalization through acylation and nucleophilic substitution produced highly phosphorylated CNOs(P-CNOs).High-resolution transmission electron microscopy(HRTEM),X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS)confirmed the successful introduction of-COOH and-PO_(3)H_(2)groups,with P-CNOs exhibiting an ion exchange capacity(IEC)of 1.85 mmol/g.Homogeneous,intact,and dense SPAES/P-CNOs composite membranes were prepared via solution casting by blending P-CNOs with sulfo‐nated poly(arylene ether sulfone)(SPAES).Compared to pristine SPAES,the composite membranes show enhanced properties including water uptake/swelling,oxidative stability,and proton conductivity.This improvement stems from hydrogen-bonding networks between the-COOH/-PO_(3)H_(2)groups in P-CNOs and the-SO_(3)H groups in SPAES,forming a more stable network structure that bolsters mechanical properties and chemical stability while facilitating proton transfer.The SPAES/P-CNOs-1.5 membrane achieves a high proton conductivity of 220 mS/cm at 90℃.At 80℃ and 100%relative humidity(RH),its maximum power density reaches 650 mW/cm^(2),36%higher than that of SPAES.It also shows excellent mechanical property and high thermal-dimensional-chemical stability,indicating significant application potential.
作者
刘莉莉
杨佩
田益嘉
黄逸瑜
张正东
闫伟
张原原
史林兴
LIU Lili;YANG Pei;TIAN Yijia;HUANG Yiyu;ZHANG Zhengdong;YAN Wei;ZHANG Yuanyuan;SHI Linxing(Jiangsu Key Laboratory of Function Control Technology for Advanced Materials,School of Science,Jiangsu Ocean University,Lianyungang 222005,China)
出处
《高等学校化学学报》
北大核心
2026年第2期136-144,共9页
Chemical Journal of Chinese Universities
基金
江苏省高等学校自然科学基金(批准号:23KJB430011)
江苏海洋大学江苏省先进材料功能调控技术重点实验室研究基金(批准号:jsklfctam202301)和江苏海洋大学研究生科研与实践创新计划项目(批准号:KYCX202503)资助。
关键词
磺化聚芳醚砜
磷酸化纳米洋葱碳
有机-无机复合
质子交换膜
燃料电池
Sulfonated poly(aryl ether sulfone)
Phosphorylated carbon nano-onions,Organic-inorganic composite
Proton exchange membrane
Fuel cell
